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states 1-(,8-HYDROXYETHYL)-2-SUBSTITUTED AMINO-2- IMIDAZOLINE David L.Garmaise, Montreal, Quebec, and Arthur F. McKay, Pointe Claire, Quebec,Canada, assiguors to Monsanto Canada Limited, La Salle, Quebec, Canada,a body politic and corporate No Drawing. Application February 20, 1956,Serial No. 566,357

4 Claims. (Cl. 260--309.6)

CHrCHaOH CH2N/ wherein R stands for an alkyl radical having from 12 to18 carbon atoms. The products of the present invention have been foundto be particularly effective in lowering surface tension.

The products of the present invention are prepared by heating a salt ofl-(B-hydroxyethyl)-2-methylmercapto- Z-imidazoline (A. F. McKay and G.R. Vavasour, Can. J. Chem. 32: 59 (1954) or its free base in an inertsolvent with a primary amine RNl-Iz wherein R stands for an alkylradical having from 12 to 18 carbon atoms. The methylmercaptan releasedduring the reaction is vented in a scrubber. On evaporation of thereaction mixture, the 1-(fi-hydroxyethyl)-2-substitutedamino-Z-imidazoline is obtained as its salt or as a free base.

If this product is obtained in the form of its salt it can be convertedto its free base by methods well known in the art, for example, bypassage of its solution through ion exchange resins. On the other hand,if it is obtained in the form of its free base, it can be converted toits acid salt by methods well known in the art.

in United States Patent 2,586,844, compounds resembling the compounds ofthe present invention are disclosed. The difference in structure is thatthe compounds of the present invention have a fl-hydroxyethyl radical inposition-1 instead of a hydrogen. The diiference is very significantsince it causes the compounds of the present invention to beparticularly useful as in lowering surface tension. The presence of the,B-hydroxyethyl improves the polar properties of the compound thusrendering the compounds of the present invention useful assurface-active agents, detergents or flotation agents. Furthermore, thepresence of the ,B-hydroxyethyl radical renders the compounds of thepresent invention useful as intermediates in the preparation ofcompounds of the formula referred to above.

The preparation of the products of the present inven- C Hat-z C-NHRCHaSHT GE -N The inert solvent used is one which will disolve bothreactants and which is non-reactive with them.

As an example of suitable alkylamines, there may be mentionedn-propylamine, n-octylamine, n-dodecylamine,

2,792,404 Patented May 14,1957,

n-tetradecylamine, n-hexadecylamine, n-octadecylamine.

The present invention will be. more fully understood by referring to thefollowing examples which should not be considered as limiting theinvention:

EXAMPLE I 1 (B-hydroxyethyl) -2- y dimethylaminopropylamino -2-imidazoline C Hz 0 H2 0 H G it-N C Ha A solution of 8.4 parts by weightof 'y-dimethylaminopropylarnine and 23.5 parts of1-(fl-hydroxethyD-2-methylmercapto-Z-imidazolinium iodide in 50 parts ofmethanol was refluxed for two hours. The evolved methyl mercaptan wasabsorbed in 20% sodium hydroxide solution. At the end of the refluxperiod, the methanol was removed by evaporation and the oily residue wasdissolved in 500 parts of water. This solution was passed through acolumn of 500 parts of activated Amberlite IRA-400 resin after which thecolumn was washed with 1500 parts of water. The combined eluate andwashing was taken to dryness in vacuo and the residue was distilled,yield 12.4 parts (71.5%). This oil (B. P. 183- 184 C./ 3 mm.) wasredistilled for analysis. Analysis of the 1-( fi-hydroxyethyl) 2('y-diethylaminopropylamino)-2-imidazoline gave 55.78% carbon and 10.43%hydrogen, compared with the theoretical calculated for C10H22N4O of56.04% carbon and 10.35 hydrogen. Its dipicrate melted at 126 C.Analysis of this dipicrate gave 20.4% nitrogen, compared with thetheoretical calculated for C22H2sN1oO15 of 20.80%.

EXAMPLE II CgHs CNHCH2CH2CH2N CH2-N/ C2115 Sixty-five parts by weight of-diethylaminopropylamine and 144 parts ofl-(fi-hydro-xyethyl)-2-methylrnercapto-2-imidazolinium iodide in 200parts of methanol were refluxed for two hours. The residue fromevaporation of the methanol was dissolved in 1000 parts of water andthis solution was passed through a column of 1500 parts of AmberliteIRA-400 resin. The aqueous eluate was taken to dryness and the residue(oily) was distilled under vacuum. An oil (B. P. 164-l65 C./0.20 mm.)was obtained in good yield. Analysis of the l-(fi-hydroxyethyl) 2('y-diethylaminopropylamino) 2 imidazolinc gave 59.21% carbon and 11.02%hydrogen, compared with the theoretical calculated for C12H26N40 of59.45% carbon and 10.82% hydrogen.

EXAMPLE III 1 -(fi-hydr0xyethyl) -2- (B-dimethylaminoethylamino -2- Asolution of 44 parts by weight of B-dimethylaminoethylamine and 139parts of l-(B-hydroxyethyl)-2-methylmercapto-Z-imidazolinium iodide in300 parts of methanol was refluxed for two hours. This reaction mixturewas evaporated in vacuo to remove the solvent and the oily residue wasdissolved in 1000 parts of water. After passing the dilute aqueoussolution through 1800 parts of Amberlite IRA-400 resin and washing thecolumn with Water, the combined eluates were taken to dryness. The 1-(fl-hydroxyethyl -2-( fi-dimethylaminoethylamino) 2-imidazoline wasobtained by distilling the residue in vacuo.

EXAMPLE IV 1 (p hydroxyethyl) 2 (p diethylaminoethylamino)-Z-imidazoline A solution of 1-( d-hydroxyethyl)-2-methylmercapto-2-imidazolinium iodide (57.6 parts) and B-diethylaminoethylamine (25.5parts) in 150 parts of methanol was refluxed until the evolution ofmethylmercaptan ceased. The solvent was removed by evaporation and theresidue was dissolved in 1000 parts of water. This aqueous solution waspassed through a column of 1000 parts of IRA-400 resin at the rate of 25parts per minute and the column was Washed with 2000 parts of water. Onevaporation of the water from the combined eluate and washings, a 90.8%yield of crude 1-(B-hydroxyethyl)-2-(B-diethylaminoethylamino)-2-imidazoline Was obtained. The dipicrate formedin the usual manner melted at 1665-167 C. This compound on analysis gave40.49% carbon, 4.67% hydrogen and 20.33% nitrogen compared with thecalculated for C23H30N10015 of 40.23% carbon, 4.40% hydrogen and 20.40%nitrogen.

EXAMPLE V 1 ()8 hydroxyethyl) 2 (n propylamino) 2 imidazoline GHQ-NCNHC3H1 UHz-N 1 (,8 hydroxyethyl) 2 methylmercapto 2 imidazoliniumiodide (86.4 parts) and n-propylamine (19.5 parts) were refluxed in 150parts by volume of methanol over a period of ninety minutes. Themethanol was removed by evaporation and the residue was dissolved in 500parts by weight of water. This aqueous solution was passed through acolumn of activated IRA-400 resin (800 parts) at the rate of 10 parts byvolume of solution per minute. Then the column was washed with 2,500parts of Water and the eluate and washings adjusted to a pH of 2.0 withhydrochloric acid solution were taken to dryness. The yield ofl-(B-hydroxyethyl) -2-n-propylamino-2-imidazolinium chloride was 90% oftheory.- Its picrate formed in the usual manner melted at 136.5 C. Thisproduct on analysis gave 49.00% carbon, 5.91% hydrogen and 12.48%nitrogen compared with the calculated for cmHzoNeOa of 49.12% carbon,5.89% hydrogen and 12.28% nitrogen.

EXAMPLE VI 1 (B hydroxyethyl) 2 n octylamino 2 imidazoline oneo'mon CH-N c-NH-omfl CHr-N A solution of 86.4 parts of 1-(B-hydroxyethyDQ-methylmercapto-2-imidazolinium iodide and 45 parts' ofnoctylamine in 150 parts of methanol was refluxed for 'two hours; Thesolution was evaporated and the residue in 800 parts of water was passedthrough a column' of IRA-400 resin (800 parts) to remove the iodide.ion.

The eluate and washings were acidified with hydrochloric acid and thentaken to dryness. 'This gave a 54.5%

yield of 1-(fr-hydroxyethyl)-2-n-octylamino-2-imidazolinium chloride.

EXAMPLE VII 1 (,8 hydroxyethyl) 2 n dodecylamino 2 imidazoline CH:OH:OH

GHQ-N O-NH-CuHai CHr-N 1 (p hydroxyethyl) 2 methylmercapto 2imidazolinium iodide (86.4 parts) and n-dodecylamine (55 parts) werecondensed in the manner described in the previous examples. Afterremoval of the methanol, the residue was dissolved in 4000 parts ofWater and then passed through a column of IRA-400 resin. The resincolumn was Washed with 6000 parts of water and the combined eluate andwashings were acidified with concentrated hydrochloric acid solution.Evaporation of the solution to dryness gave a 86.5% yield of thel-(B-hydroxyethyl) 2 n dodecylarnino 2 imidazolinium chloride. Thephenylisothiocyanate derivative formed in the usual manner melted at100l02 C. This derivative on analysis gave 66.61% carbon, 9.38%hydrogen, 13.15% nitrogen and 7.20% sulfur compared with the calculatedfor Carl-140N408 of 66.61% carbon, 9.32% hydrogen, 12.95% nitrogen and7.41% sulfur.

. EXAMPLEVIII V 1 (B -hydroxyethyl) 2 n tetradecylamine 2- imidazolineCHr-N I CNH-Cr4H2c GET- A solution ofl-(B-hydroxyethyl)-2-methylmercapto-2- imidazolinium iodide (86.4 parts)and 63.9 parts of ntetradecylamine in 200 parts of methanol was refluxedfor threehours. This solution was diluted with 300 parts of methanol andthen it was passed through a column of IRA-400 (1000 parts of resinpreviously washed with. 800 parts of methanol). The column was washedwith methanol until the methanol solutions no longer gave a picrate. Thecombined eluate and washings then were taken to dryness, yield 97.5parts (100%) of l (B hydroxyethyl 2 n tetradecylamino 2 imidaz-I-(B-hydroxyethyl) -2- (n-hexadecylamino) -2-imidaz0line C 1512- C H2O HCRT-N C-NH-CreHzs 'A solution of 1-(p -hydroxyethyl)-2-methylrnercapto-Z-imidazolinium iodide (57.6 parts) and n-hexadecylamine (48.2 parts) in200 parts of methanol was refluxed for three hours. This solution wasdiluted with 250 parts of methanol and; then passed through a column ofIRA-400 resin (1200 parts) which had been'washed previously withmethanol. The column Was washed with V 2000 parts of methanol and theeluate and washings were taken to dryness.

The yield of I-(B hydrOXyethyD-Z- (Ehexadecylamino)-2-imidazoline, was70.5 parts by weight or 99.9%.. The'dibenzoyl-D-tartrate salt (M. P.

110-111 C.) of 1-(B-hydroxyethyl)-2-(n-hexadecylamino)-2-imidazoline wasformed in the usual manner. This salt on analysis gave 66.17% carbon,8.29% hydrogen and 6.01% nitrogen compared with the calculated forCasHszNaOn of 65.80% carbon, 8.07% hydrogen and 5.90% nitrogen.

EXAMPLE X 1- (,S-hydroxyethyl) -2-( n-octadecylamino) -2-imidaz0line 6We claim: 1. As new productsl-(B-hydroxyethyl)-2-substitutedamino-2-irnidazoline corresponding tothe general formula:

wherein R stands for an alkyl radical having from 12 to 18 carbon atoms,and their acid salts.

2. 1 (18-hydroxyethyl)-2-(n-dodecylamino)-2-imidazoline.

3. l-(fl-hydroxyethyl)-2-(n-tetradecylamino)-2-imidazoline.

4. 1-( B-hydroxyethyi) -2- (n-octadecylamino) -2-imidazoline.

References Cited in the file of this patent UNITED STATES PATENTS McKayet a1. Feb. 26, 1952 Cain Aug. 16, 1955

1. AS NEW PRODUCTS 1-(B-HYDROXYETHYL)-2-SUBSTITUTEDAMINO-2-IMIDAZOLINECORRESPONDING TO THE GENERAL FORMULA: